Electrode body, electrolytic capacitor provided with electrode body, and method for producing electrode body

ABSTRACT

Provided is an electrode body that exhibits a good cathode side capacitance, and an electrolytic capacitor provided with this electrode body. The electrode body used for a cathode of the electrolytic capacitor has a cathode foil and a carbon layer. The cathode foil is made of a valve acting metal, and an enlarged surface layer is formed on the surface thereof. The carbon layer is formed on the enlarged surface layer. The interface between the enlarged surface layer and the carbon layer has an uneven shape.

RELATED APPLICATIONS

This application is a continuation of prior U.S. application Ser. No.17/057,545, filed on Nov. 20, 2020, which was the National Stage ofInternational Application No. PCT/JP2019/022741, filed on Jun. 7, 2019,which claims priority to Japanese Application No. 2018-111486, filed onJun. 11, 2018, the entire contents of each of which being incorporatedby reference herein.

TECHNICAL FIELD

The present disclosure relates to an electrode body, an electrolyticcapacitor having the electrode body, and a method for manufacturing theelectrode body.

BACKGROUND ART

The electrolytic capacitor includes a valve acting metal such astantalum or aluminum as an anode foil and a cathode foil. The anode foilis enlarged by forming the valve acting metal into a shape such as asintered body or an etching foil, and has a dielectric oxide film layeron the enlarged surface. An electrolytic solution is interposed betweenthe anode foil and the cathode foil. The electrolytic solution is inclose contact with the uneven surface of the anode foil and functions asa true cathode. In this electrolytic capacitor, a capacitance on theanode side is obtained by a dielectric polarization action of thedielectric oxide film layer.

The electrolytic capacitor can be regarded as a series capacitor inwhich capacitance is emerged on the anode side and the cathode side.Therefore, the cathode side capacitance is very important to efficientlyutilize the anode side capacitance. Therefore, although the surface areaof the cathode foil is increased by, for example, the etching treatment,there is a limit to the enlargement of the cathode foil from theviewpoint of the thickness of the cathode foil.

Therefore, the electrolytic capacitor in which a film of a metal nitridesuch as titanium nitride is formed on the cathode foil has been proposed(see Patent Document 1). Under a nitrogen gas environment, titanium isevaporated by a vacuum arc deposition method, which is a kind of ionplating method, and titanium nitride is deposited on the surface of thecathode foil. The metal nitride is inert, and it is difficult to form anatural oxide film. In addition, the deposited film is formed with fineunevenness and the surface area of the cathode is enlarged.

The electrolytic capacitor in which a porous carbon layer includedactivated carbon is formed on the cathode foil has been proposed (seePatent Document 2). A capacitance of the cathode side in thiselectrolytic capacitor is emerged by a storage action of the electricdouble layer formed on a boundary surface between a polar electrode andan electrolyte. Cations of the electrolyte are aligned at the boundarysurface with the porous carbon layer and paired with electrons in theporous carbon layer at a very short distance, forming a potentialbarrier at the cathode. The cathode foil on which this porous carbonlayer is formed is produced by kneading a water-soluble binder solutionin which porous carbon is dispersed to form a paste, applying the pasteto the surface of the cathode foil, and drying the paste by exposing itto a high temperature.

CITATION LIST Patent Literature

-   Patent Document 1: JP H04-61109 A-   Patent Document 2: JP 2006-80111 A

SUMMARY OF DISCLOSURE Technical Problem

The deposition process of metal nitrides is complicated and difficult tointroduce industrially, resulting in high cost and deterioration ofyield of the electrolytic capacitors. The electrolytic capacitor inwhich the porous carbon layer containing the activated carbon is formedon the cathode foil by applying the paste has a lower capacitance in anormal temperature environment and a high temperature environment thanthe electrolytic capacitor in which the metal nitride is deposited onthe cathode foil. Therefore, in the electrolytic capacitor in which theporous carbon layer is formed on the cathode foil by applying the paste,a satisfactory capacitance has not yet been obtained.

The present disclosure has been proposed to solve the above problems,and an objective of the present disclosure is to provide an electrodebody that emerges good capacitance, an electrolytic capacitor having theelectrode body, and a method for manufacturing the electrode body.

Solution to Problem

In order to solve the above problems, the electrode body according tothe present invention is an electrode body used for a cathode of anelectrolytic capacitor which includes a cathode foil made of a valveacting metal, having an enlarged surface layer formed on a surface, anda carbon layer formed on the enlarged surface layer, in which aninterface between the enlarged surface layer and the carbon layer has anuneven shape.

An unevenness depth of the uneven shape may be 0.5 μm or more.

The enlarged surface layer may be formed by digging a plurality ofetching pits, a diameter of the etching pit may be 0.12 μm or more and0.43 μm or less near a surface layer, a depth of the etching pit may be1.5 μm or more and 5.0 μm or less, in the uneven shape, a distancebetween both ends in a cross section obtained by cutting a convex regionalong a height direction may be 1.5 μm or more and 8.0 μm or less, andthe uneven shape may have a convex region height of 0.15 μm or more and0.80 μm or less.

The enlarged surface layer may be formed by digging a plurality ofetching pits, and the carbon layer further enters the etching pit froman interface of the uneven shape.

The carbon layer that further enters the etching pit from a concaveregion may penetrate from an apex of the convex region adjacent to theconcave region to a position that sinks by an average of 0.5 μm or morein a depth direction.

The carbon layer that further enters the etching pit from a concaveregion may penetrate from an apex of the convex region adjacent to theconcave region to a position that sinks by an average of 0.7 μm or morein a depth direction.

The enlarged surface layer may be formed by digging a plurality ofetching pits, and a ratio of an interface length Y to a range length X(Y/X×100) is 110% or more. Here, the interface length Y is a length froman arbitrary start point to an arbitrary end point along the interfacebetween the enlarged surface layer and the carbon layer, and is a lengthincluding the carbon layer entering the etching pit, and the rangelength X is, among vectors connecting the start point and the end pointat which the interface length Y is measured in a straight line, a lengthof a direction component orthogonal to the height direction of theuneven shape.

The uneven shape may be compressed and deformed by pressing.

The carbon layer may contain a scaly carbon material and a sphericalcarbon material.

An electrolytic capacitor having this electrode body as the cathode isalso an aspect of the present invention.

In addition, a method for manufacturing an electrode body used for acathode of an electrolytic capacitor, includes steps of,

-   -   forming a carbon layer on a cathode foil made of a valve acting        metal and having an enlarged surface layer formed on a surface,        and pressing the cathode foil on which the carbon layer is        formed, in which an interface between the enlarged surface layer        and the carbon layer has an uneven shape.

The cathode foil on which the carbon layer is formed may be pressed witha press line pressure of 1.54 kNcm⁻¹ or more.

The carbon layer may be formed by applying a slurry containing scalycarbon and spherical carbon to the cathode foil and drying it.

Advantageous Effects of Disclosure

According to the present invention, even when the carbon layer is usedfor the cathode body, good capacitance can be emerged.

BRIEF DESCRIPTION OF DRAWINGS

FIGS. 1A and 1B are schematic views illustrating an interface structurebetween an enlarged surface layer and a carbon layer of the electrodebody according to the present embodiment.

FIGS. 2A and 2B are SEM images of Comparative Example 1, in which FIG.2A shows no press and FIG. 2B shows a press line pressure of 3.85kNcm⁻¹.

FIG. 3 is an SEM image of Comparative Example 2.

FIGS. 4A and 4B are SEM images of Example 1.

FIGS. 5A and 5B are SEM images of Example 2.

FIGS. 6A and 6B are SEM images of Example 3.

FIGS. 7A and 7B are SEM images of Example 5.

FIGS. 8A and 8B are SEM images of Example 8.

FIGS. 9A-9C are SEM images of the cathode foil in which the carbon layerdoes not exist.

DESCRIPTION OF EMBODIMENTS

The cathode body and the electrolytic capacitor including the cathodebody according to the embodiment of the present invention will bedescribed. In the present embodiment, an electrolytic capacitor havingan electrolytic solution will be described as an example, however thepresent disclosure is not limited thereto. It can be applied to anyelectrolytic capacitor having the electrolytic solution, a solidelectrolyte layer such as a conductive polymer, a gel electrolyte, or anelectrolyte in which an electrolytic solution is used in combinationwith the solid electrolyte layer and the gel electrolyte.

(Electrolytic Capacitor)

The electrolytic capacitor is a passive element that stores anddischarges electric charges according to the capacitance. Thiselectrolytic capacitor has a wound type or a laminated type capacitorelement. The capacitor element is formed by facing the anode foil andthe cathode body via a separator, and then impregnating with theelectrolytic solution. In this electrolytic capacitor, the cathode sidecapacitance is generated by an electric double layer action generated atthe boundary surface between the electrolytic solution and the cathodebody, and the anode side capacitance is generated by a dielectricpolarization action.

That is, a dielectric oxide film layer that causes the dielectricpolarization action is formed on the surface of the anode foil. On thesurface of the cathode body, a carbon layer that causes the electricdouble layer action at the boundary surface with the electrolyticsolution is formed. The electrolytic solution is interposed between theanode foil and the cathode body, and is in close contact with thedielectric oxide film layer of the anode foil and the carbon layer ofthe cathode body. The separator is interposed between the anode foil andthe cathode body and holds the electrolytic solution in order to preventa short circuit between the anode foil and the cathode body.

When a solid electrolyte is used, the solid electrolyte is conducted bythe carbon layer in contact with a current collector, and thecapacitance on the anode side by the dielectric polarization actionconstitutes the capacitance of the electrolytic capacitor.

(Cathode Body)

This cathode body has a two-layer structure of the cathode foil and thecarbon layer. The cathode foil serves as the current collector, and anenlarged surface layer is formed on the surface thereof. The carbonlayer includes a carbon material and adheres to the enlarged surfacelayer of the cathode foil.

The cathode foil is a long foil body made of a valve acting metal. Thevalve acting metal is aluminum, tantalum, niobium, niobium oxide,titanium, hafnium, zirconium, zinc, tungsten, bismuth, antimony and thelike. The purity is preferably about 99% or more, however impuritiessuch as silicon, iron, copper, magnesium, and zinc may be contained. Asthe cathode foil, for example, an aluminum material having a temperdesignation of H defined in JIS standard H0001, a so-called H material,or an aluminum material having a temper designation of O defined in JISstandard H0001, a so-called O material, may be used. When a highly rigidmetal foil made of H material is used, deformation of the cathode foildue to press working described later can be suppressed.

In this cathode foil, an enlarging treatment is applied to the metalfoil in which the valve acting metal is stretched. The enlarged surfacelayer is formed by electrolytic etching, chemical etching, sandblasting,or the like, or by depositing or sintering metal particles or the likeon the metal foil. Examples of the electrolytic etching include methodssuch as DC etching and AC etching. In chemical etching, the metal foilis immersed in an acid solution or an alkaline solution. The formedenlarged surface layer is a layer region having a tunnel-shaped etchingpit dug from the foil surface toward the foil core portion or asponge-shaped etching pit. Note that the etching pit may be formed so asto penetrate the cathode foil.

In the carbon layer, the carbon material is fibrous carbon, carbonpowder, or a mixture thereof. The fibrous carbon is a carbon nanotube, acarbon nanofiber, or the like. The carbon nanotube may be asingle-walled carbon nanotube in which the graphene sheet is one layer,or a multi-walled carbon nanotube (MWCNT) in which two or more layers ofgraphene sheets are coaxially rolled and the tube wall is multi-walled.The carbon powder is natural plant tissue such as coconut shell,synthetic resin such as phenol, activated carbon made from fossil fuelsuch as coal, coke, pitch, etc., carbon black such as Ketjen black,acetylene black, channel black, carbon nanohorn, amorphous carbon,natural graphite, artificial graphite, graphitized Ketjen black,mesoporous carbon, etc. In the electrolytic capacitor using theelectrolytic solution as the electrolyte, it is preferable that thecarbon material exhibits an electric double layer action.

The fibrous carbon or the carbon powder may be subjected to a poreforming treatment such as an activation treatment or an openingtreatment for forming pores. The method for activating the carbon powdervaries depending on the raw material to be used, however usually, aconventionally known activation treatment such as a gas activationmethod or a chemical activation method can be used. Examples of the gasused in the gas activation method include water vapor, air, carbonmonoxide, carbon dioxide, hydrogen chloride, oxygen, or a gas composedof a mixture thereof. In addition, the chemicals used in the chemicalactivation method include alkali metal hydroxides such as sodiumhydroxide and potassium hydroxide, alkaline earth metal hydroxides suchas calcium hydroxide, inorganic acids such as boric acid, phosphoricacid, sulfuric acid and hydrochloric acid, and inorganic salts such aszinc chloride. During this activation treatment, heat treatment isperformed as necessary.

FIG. 1A is a schematic view illustrating a surface in which the cathodefoil and the carbon layer are in contact, that is, an interfacestructure between the enlarged surface layer and the carbon layer. Sincethe carbon layer (reference number 2 in the figure) enters the etchingpit (reference number 1 in the figure), a part of the interface betweenthe enlarged surface layer (reference number 3 in the figure) and thecarbon layer has fine uneven shape along the etching pit. Hereinafter,the uneven shape in which the carbon layer has entered the etching pitis referred to as etching unevenness (reference number 4 in the figure).

At the interface between the enlarged surface layer and the carbonlayer, apart from the etching unevenness, undulating unevenness, thatis, unevenness having a long wavelength is generated. Hereinafter, thisunevenness is referred to as an outer surface unevenness (referencenumber 5 in the figure). In other words, assuming that there are noetching pits, the surface of the enlarged surface layer constitutesundulations by connecting convex regions having wide bases to concaveregions, and the carbon layer is in close contact with the undulations.The etching unevenness extends continuously toward deep part from theconvex region and the concave region of the outer surface unevenness.The outer surface unevenness brings a three-dimensional structure to thesurface of the enlarged surface layer and increases the contact areawith the carbon layer.

Here, in an aging step of the electrolytic capacitor, an oxide film isformed on exposed portion of the surface of the enlarged surface layer.Further, the increase in the contact area between the enlarged surfacelayer and the carbon layer leads to a decrease in the exposed portion ofthe surface of the enlarged surface layer. Then, the outer surfaceunevenness that increases the contact area between the enlarged surfacelayer and the carbon layer reduces the area where the oxide film isformed as the entire cathode foil in the aging step. Therefore, comparedto the electrolytic capacitor using the cathode foil deposited withtitanium nitride, the electrolytic capacitor using the cathode bodyhaving the outer surface unevenness at the interface between theenlarged surface layer and the carbon layer increases the capacitancedue to charging and discharging in a high frequency region such as 10kHz, and the reduction rate of the capacitance in a high thermalenvironment such as 125° C. is also suppressed.

In particular, an appropriate intricacy of the outer surface unevennessenhances the effect of increasing the contact area between the enlargedsurface layer and the carbon layer. First, the oxide film is formed onthe surface of the enlarged surface layer naturally or due to theelectrolytic solution, however when the carbon layer is formed on theenlarged surface layer and pressed, the carbon material of the carbonlayer is thrust against the surface of the enlarged surface layer,breaks the oxide film, and the unoxidized enlarged surface layer and thecarbon layer come into direct contact with each other. Secondly, theforce for further pushing the carbon layer in the concave region intothe etching pit is easily transmitted, and the carbon layer penetratesinto the enlarged surface layer by the depth including the concaveregion and the etching pit, the contact area between the carbon layerand the enlarged surface layer is further increased, and the resistanceof the cathode body can be reduced.

On the other hand, when the intricacy becomes complicated to a certainextent, it becomes difficult to transmit the force for further pushingthe carbon layer that has entered the concave region into the etchingpit. Therefore, when the intricacy becomes complicated to the certainextent, the capacitance is improved, however the degree of improvementis limited.

The outer surface unevenness having the appropriate intricacy are asfollows. First, the unevenness depth Hf of the outer surface unevennessis preferably 0.5 μm or more. The unevenness depth Hf of the outersurface indicates the distance to the deepest concave portion of theouter surface unevenness with reference to a flat line L which is a lineconnecting the two vertices of the outer surface unevenness. The crosssection of the cathode body may be photographed with a scanning electronmicroscope, and the distance to the deepest concave portion may bemeasured with reference to the flat line connecting the two highestconvex portions of the outer surface unevenness on the SEM image. Bysetting the unevenness depth Hf of the outer surface to 0.5 μm or more,the adhesion to the carbon layer is enhanced.

The length Lc of the convex region of the outer surface unevenness is inthe range of 1.5 μm or more and 8.0 μm or less, and the average is about2.9 μm to 4.0 μm, and the height Hc of the convex region of the outersurface unevenness is in the range of 0.15 μm or more and 0.80 μm orless, and the average is about 0.3 μm to 0.6 μm. The length Lc of theconvex region is the distance between both ends in a cross sectionobtained by cutting the convex region along the height direction. Thelength Ld of the concave region is in the range of 2.0 μm or more and7.7 μm or less, and the average is about 3.8 μm. Regarding eachnumerical value representing the outer surface unevenness, the crosssection of the cathode body may be photographed with a scanning electronmicroscope and measured it on the SEM image. The average may be measuredby extracting 5 points.

However, even in this range, when the undulation of the outer surfaceunevenness is significant, that is, when the length Lc of the convexregion of the outer surface unevenness is in the range of 3.77 μm orless, compared with the cathode body deposited with titanium nitride,the superiority in terms of capacitance deterioration during use in ahigh thermal environment such as 125° C. and in a high frequency regionsuch as 10 kHz is reduced. On the other hand, when the undulation of theouter surface unevenness becomes gentle, that is, when the outer surfaceunevenness is present however the length Lc of the convex region of theouter surface unevenness is 3.78 μm or more, compared with the cathodebody deposited with titanium nitride, the superiority in terms ofcapacitance deterioration during use in a high thermal environment suchas 125° C. and in a high frequency region such as 10 kHz is great.

The deepest distance Hd of the carbon layer pushed further into theetching pit from the interface in the concave region by the outersurface unevenness is 0.42 μm or more and 1.40 μm or less in the depthdirection from the apex of the convex region adjacent to the concaveregion, and the average is about 0.54 μm to 0.96 μm. When the outersurface unevenness is gentle, the average is 0.7 μm or more. When it is0.5 μm or less, the effect of improving the capacitance is small. Whenit is 0.7 μm or more, it has a good capacitance and high thermalstability. Thermal stability means that there is little deterioration ofcapacitance in the high temperature environment.

The etching pit has a diameter De in the range of 0.12 μm or more and0.43 μm or less in the vicinity of the surface, and has an averagediameter of about 0.25 μm. Further, the etching pit by the etchingtreatment has a depth He in the range of 1.5 μm or more and 5.0 μm orless, and has an average depth of about 3.3 μm.

Further, another index is shown for the outer surface unevenness havingthe appropriate intricacy. FIG. 1B is a cross-sectional view cut alongthe height direction of the unevenness, in other words, across-sectional view cut along the thickness direction of the cathodebody from the surface of the cathode body toward the deep part. In thiscross section, the length along the interface between the enlargedsurface layer and the carbon layer from an arbitrary start point to anarbitrary end point is defined as the interface length Y. This interfacecontains the carbon layer that enters the etching pit. Further, amongthe vectors connecting the start point and the end point at which theinterface length Y is measured in a straight line, a range length X is alength of the direction component in which the height of the unevennessis constant, that is, the direction component orthogonal to the heightdirection of the unevenness.

At this time, the ratio of the interface length Y to the range length Xis preferably 110% or more. Less than 110% indicates that almost noouter surface unevenness is formed, when there is no load at 20° C.,each charging/discharging capacitance at 120 Hz and 10 kHz afterapplying a DC 2.4V load for 250 hours under a 125° C. environment isinferior to that of an electrolytic capacitor made of the cathode bodydeposited with titanium nitride.

Further, it is preferable that most of the voids in the carbon layerdisappear and the carbon layer is dense. The porosity of the carbonlayer is preferably less than 18%. Since the porosity of the carbonlayer is small, the adhesion between the carbon layer and the etchingsurface is improved. The porosity of the carbon layer is calculated by(area of the carbon layer void portion/area of the entire carbonlayer)×100. The porosity can be calculated by analyzing eachcross-sectional SEM image (observation magnification: 25,000 times)using an image analysis software ImageJ (NIH, National Institutes ofHealth).

A method of forming an interface structure having the outer surfaceunevenness and the etching unevenness will be illustrated. However, themethod is not limited to the illustrated method as long as the interfacestructure is composed of the outer surface unevenness and the etchingunevenness. For example, the etching pits may be removed from thesurface of the enlarged surface layer by another method such as shotpeening to form unevenness with undulations.

First, the surface enlarged layer is formed on the cathode foil.Typically, the enlarged surface layer is formed by direct currentetching or alternating current etching in which direct current oralternating current is applied in an acidic aqueous solution such asnitric acid, sulfuric acid, or hydrochloric acid.

Regarding the carbon layer, the powder of the carbon material isdispersed in a solvent, and a binder is added to prepare a slurry.Solvents include alcohols such as methanol, ethanol, and 2-propanol,hydrocarbon solvents, aromatic solvents, amide solvents such asN-methyl-2-pyrrolidone (NMP) and N, N-dimethylformamide (DMF), water andmixtures thereof. As the dispersion method, a mixer, jet mixing (jetcollision), ultracentrifugation treatment, or other ultrasonic treatmentis used. In the dispersion step, the carbon material powder and thebinder in the mixed solution are subdivided and homogenized anddispersed in the solution. Examples of the binder includestyrene-butadiene rubber.

Next, the slurry is applied to the enlarged surface layer, dried, andthen pressed at a predetermined pressure to contact the cathode foil andthe carbon layer into closely with each other and integrate them. It isconsidered that the interface structure between the enlarged surfacelayer and the carbon layer is formed in the pressing process in whichthe cathode foil and the carbon layer are brought into close contactwith each other.

In this pressing process, the carbon material of the carbon layer ispressed against the enlarged surface layer, and the entire surface ofthe cathode foil is compressed and deformed. Further, the dense regionof the etching pit is greatly compressed and deformed. As a result, thesurface state of the smooth cathode foil is deformed, and undulatingunevenness are created at the interface between the enlarged surfacelayer and the carbon layer. In addition, at the same time as theappearance of the unevenness, the enlarged surface layer and the carbonlayer are in close contact with each other. Furthermore, the carbonmaterial breaks through the natural oxide film existing on the surfaceof the cathode foil and comes into direct contact with the cathode foil.In this way, after the pressing process of a predetermined pressure isperformed, the formation of the outer surface unevenness and the closecontact between the enlarged surface layer and the carbon layer areachieved at the same time, and a gap is less likely to occur between theundulating enlarged surface layer and the carbon layer.

In this pressing step, for example, press line pressure is applied tothe cathode foil coated with the carbon layer by a press roller. At thistime, the press roller to which heat equal to or higher than thesoftening temperature of the binder contained in the carbon layer isapplied may be used. By doing so, the fluidity of the carbon layer isincreased. Therefore, the carbon layer easily enters the etching pit,the contact area between the carbon layer and the cathode foilincreases, and the interfacial resistance becomes lower.

Further, a gentle outer surface unevenness is formed by press working atthe predetermined pressure, and the gentle outer surface unevennessmakes it easy for the press pressure to be transmitted to the carbonlayer in the concave region, and the carbon layer in the concave regionfurther becomes easier to enter the etching pit. Further, the carbonlayer is compressed by the press working, and the voids in the carbonlayer are easily eliminated. It is desirable that the linear pressure bythe press presses so that the carbon material penetrates the naturaloxide film existing on the surface of the cathode foil and comes intodirect contact with the cathode foil, specifically, 1.54 kNcm⁻¹ or moreis desirable, and more preferably 3.85 kNcm⁻¹ or more. When the pressline pressure is 1.54 kNcm⁻¹ or more, the outer surface unevenness isformed, and when the press line pressure is 3.85 kNcm⁻¹ or more, theouter surface unevenness becomes gentle.

The carbon material that assists in the change of the interfacestructure is preferably a mixture of a scaly carbon material and aspherical carbon material. The scaly carbon material is easy to pressagainst the enlarged surface layer, is easily and orderly spread on theinterface with the enlarged surface layer, and is easily pushed againstthe natural oxide film on the foil surface by press bonding, and easilybreaks through the natural oxide film. Therefore, the scaly carbonmaterial is easy to mold the interface structure into uneven shape withundulations, and is easy to adhere to the cathode foil at the interface.In addition, the scaly carbon material tends to be orderly stacked atthe interface of the enlarged surface layer. Therefore, the scaly carbonmaterial reduces the voids in the carbon layer. The spherical carbonmaterial fills the voids in the carbon layer and easily enters theetching pit during the bonding process with the cathode foil.

Examples of the scaly carbon material include natural graphite,artificial graphite, and graphitized Ketjen black. It is desirable touse the scaly carbons having an aspect ratio of the minor radius to themajor radius in the range of 1:5 to 1:100. Examples of the sphericalcarbon material include carbon black such as Ketjen black (hereinafter,KB), acetylene black, and channel black. The primary particle size ofcarbon black is preferably 100 nm or less, and it is easy to enter thedeep part of the etching pit. In general, these scaly carbon materialsand spherical carbon materials have a smaller specific surface area anda smaller electric double layer capacity than activated carbon andcarbon nanotubes, and therefore generally serve as a conductiveauxiliary agent rather than an active material. However, in thiselectrolytic capacitor, a sufficient cathode side capacitance is drawnout due to the interface structure between the enlarged surface layerand the carbon layer, that is, the generation of the outer surfaceunevenness or the further generation of the etching unevenness.

Of course, in addition to these scaly carbon materials and sphericalcarbon materials, activated carbon, carbon nanotubes, and the like maybe contained, and only these scaly carbon materials and spherical carbonmaterials may be contained in the carbon layer as active materials.Activated carbon and carbon nanotubes have a large specific surface areadue to delocalized pi electrons. In addition, in this electrolyticcapacitor, since a sufficient cathode side capacitance is drawn out dueto the outer surface unevenness or the etching unevenness on theinterface between the enlarged surface layer and the carbon layer, thescaly carbon materials and the spherical carbon materials may not besubjected to the pore forming treatment. Of course, the scaly carbonmaterials and the spherical carbon materials may also be used afterbeing subjected to a pore forming treatment.

(Anode Foil)

The anode foil is a long foil body made of a valve acting metal. Thepurity is preferably about 99.9% or more with respect to the anode foil.This anode foil is formed by etching a stretched foil, sintering powderof the valve acting metal, or depositing a film of metal particles orthe like on the foil to apply the film. The anode foil has an enlargedsurface layer or a porous structure layer on a surface.

A dielectric oxide film layer formed on the anode foil is typically anoxide film formed on the surface layer of the anode foil, and when theanode foil is made of aluminum, it is an aluminum oxide layer obtainedby oxidizing a porous structural region. This dielectric oxide filmlayer is formed by a formation treatment in which a voltage is appliedin an acid such as ammonium borate, ammonium phosphate, ammoniumadipate, or a solution in the absence of halogen ions such as an aqueoussolution of these acids. The natural oxide film layer may be formed onthe cathode foil, and the dielectric oxide film layer may beintentionally provided.

(Separator)

Separator includes celluloses such as kraft, Manila hemp, esparto, hemp,and rayon, and mixed papers thereof, polyethylene terephthalates,polybutylene terephthalates, polyethylene naphthalates, polyester resinssuch as derivatives thereof, polytetrafluoroethylene resins,polyvinylidene fluoride resin, vinylon resin, aliphatic polyamide,semi-aromatic polyamide, polyamide resin such as total aromaticpolyamide, polyimide resin, polyethylene resin, polypropylene resin,trimethylpentene resin, polyphenylene sulfide resin, acrylic resin andthe like, these resins may be used alone or in combination.

(Electrolytic Solution)

The electrolytic solution is a mixed solution in which a solute isdissolved in a solvent and additives are added as needed. The solventmay be water, a protic organic polar solvent or an aprotic organic polarsolvent. Typical examples of the protic organic polar solvents includemonohydric alcohols, polyhydric alcohols, and oxyalcohol compounds.Typical examples of the aprotic organic polar solvents includesulfone-based, amide-based, lactones, cyclic amide-based, nitrile-based,and oxide-based solvents.

Examples of the monohydric alcohols include ethanol, propanol, butanol,pentanol, hexanol, cyclobutanol, cyclopentanol, cyclohexanol, benzylalcohol and the like. Examples of the polyhydric alcohols and theoxyalcohol compounds include ethylene glycol, propylene glycol,glycerin, methyl cellosolve, ethyl cellosolve, methoxypropylene glycol,dimethoxypropanol and the like. Examples of the sulfone-based includedimethyl sulfone, ethyl methyl sulfone, diethyl sulfone, sulfolane,3-methyl sulfolane, 2,4-dimethyl sulfolane and the like. Examples of theamide-based include N-methylformamide, N, N-dimethylformamide,N-ethylformamide, N, N-diethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide andhexamethylphosphoricamide and the like. Examples of the lactones and thecyclic amide-based include γ-butyrolactone, γ-valerolactone,δ-valerolactone, N-methyl-2-pyrrolidone, ethylene carbonate, propylenecarbonate, butylene carbonate, isobutylene carbonate, isobutylenecarbonate and the like. Examples of the nitrile-based includeacetonitrile, 3-methoxypropionitrile, glutaronitrile and the like.Examples of the oxide-based include dimethyl sulfoxide and the like. Asthe solvent, these may be used alone, or two or more kinds may becombined.

The solute contained in the electrolytic solution contains anionic andcationic components, and is typically an organic acid or a salt thereof,an inorganic acid or a salt thereof, or a composite compound of theorganic acid and the inorganic acid or a salt having an ion dissociativeproperty thereof, and is used alone or in combination of two or more. Anacid as an anion and a base as a cation may be separately added to theelectrolytic solution as solute components.

Organic acids that become anionic components in the electrolyticsolution include oxalic acid, succinic acid, glutaric acid, pimelicacid, suberic acid, sebacic acid, phthalic acid, isophthalic acid,terephthalic acid, maleic acid, adipic acid, benzoic acid, and toluylacid, enanthic acids, malonic acids, carboxylic acids such as1,6-decandicarboxylic acid, 1,7-octanedicarboxylic acid, azelaic acid,undecanedioic acid, dodecanedioic acid, tridecanedioic acid, phenols andsulfonic acids. Examples of the inorganic acid include boric acid,phosphoric acid, phosphorus acid, hypophosphorous acid, carbonic acid,silicic acid and the like. Examples of the composite compound of theorganic acid and the inorganic acid include borodisalicylic acid,borodioxalic acid, and borodiglycolic acid.

Further, examples of at least one salt of the organic acid, theinorganic acid, and the composite compound of the organic acid and theinorganic acid include ammonium salts, quaternary ammonium salts,quaternary amidinium salts, amine salts, sodium salts, and potassiumsalts, and the like. Examples of the quaternary ammonium ion of thequaternary ammonium salts include tetramethylammonium,triethylmethylammonium, tetraethylammonium and the like. Examples of thequaternary amidiniums include ethyldimethylimidazolinium andtetramethylimidazolinium. Examples of amines in the amine salts includeprimary amines, secondary amines, and tertiary amines. Primary aminesinclude methylamine, ethylamine and propylamine, secondary aminesinclude dimethylamine, diethylamine, ethylmethylamine and dibutylamine,and tertiary amines include trimethylamine, triethylamine,tributylamine, ethyldimethylamine, and ethyldiisopropylamine and thelike.

Further, other additives may be added to the electrolytic solution.Additives include polyethylene glycol, complex compounds of boric acidand polysaccharides (mannit, sorbit, etc.), complex compounds of boricacid and polyhydric alcohol, borate esters, nitro compounds(o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid,o-nitrophenol, m-nitrophenol, p-nitrophenol, etc.), phosphate esters andthe like. These may be used alone, or two or more kinds may be combined.

When a solid electrolyte is used as the electrolyte, polythiophene suchas polyethylenedioxythiophene and conductive polymers such aspolypyrrole and polyaniline can be mentioned.

Examples

Hereinafter, the present invention will be described in more detailbased on Examples. The present invention is not limited to the followingexamples.

(Cathode Body)

First, various cathode bodies were prepared. The aluminum foil shown inTable 1 below was prepared as the cathode foil. In Table 1, the etchingmagnification indicates a magnification of a surface area after theetching treatment to a surface area of a plane which is a surface areabefore the etching treatment. The etched layer thickness indicates anaverage depth from the surface to the deepest part of the etching pit.The residual core thickness indicates a thickness of the layer to whichthe etching pit has not reached. The oxide film is indicated by anominal formation voltage. That is, with respect to the cathode foils ofa foil type 1, a foil type 2 and a foil type 4, a voltage was appliedwith an aqueous solution of ammonium dihydrogen phosphate tointentionally form the oxide film layer. The formation treatment was notperformed for the cathode foil of a foil type 3.

TABLE 1 Foil type Foil type 1 Foil type 2 Foil type 3 Foil type 4 Foil20 21 21 30 thickness (μm) Etching 1 7 17 22 magnification Etched layer0 6 8 11 thickness (μm) Residual core 20 15 13 19 thickness (um) Oxidefilm (V_(fs)) 1.2 1.2 0 1.2

A slurry was prepared under common conditions for the carbon layerformed on the cathode foil of each foil type in Table 1. 16.3 g ofgraphite was selected as the scaly carbon material, 5 g of carbon blackwas selected as the spherical carbon material, and 3.7 g ofstyrene-butadiene rubber was selected as the binder. Then, these wereadded to 75 ml of pure water adjusted to pH 8 with ammonia, anddispersed by a stirrer. This slurry was applied to each cathode foil anddried at 100° C. The particle size of graphite is 4 μm, the primaryparticle size of carbon black is 35 nm, and the activation treatment orthe opening treatment was not performed for both.

Then, as shown in Table 2 below, by applying each press line pressure toeach cathode foil coated with the carbon layer, various cathode bodieshaving different etching treatment and press line pressure wereproduced. For the press line pressure, a press machine manufactured byTakumi Giken Co., Ltd. was used. In this pressing process, the diameterof the press roller was 180 mm, the press processing width was 130 mm,and the cathode body was conveyed once at 3 m/min.

TABLE 2 Press line Foil Etching pressure type magnification (KNcm⁻¹)Comparative 1 1 0 Example 1 1.54 3.85 7.69 Comparative 2 7 0 Example 2Example 1 1.54 Example 2 3.85 Example 10 5.38 Example 3 7.69 Comparative3 17 0 Example 3 Example 4 1.54 Example 5 3.85 Example 6 7.69Comparative 4 22 0 Example 4 Example 7 1.54 Example 8 3.85 Example 97.69

As shown in Table 2, an electrolytic capacitor using the unetched foiltype 1 is referred to as Comparative Example 1 regardless of the pressline pressure. Among electrolytic capacitors using foil type 2 having anetching magnification of 7 times, unpressed capacitor is referred to asComparative Example 2, then capacitors are referred to as Examples 1 to3 in ascending order of the press line pressure, and the capacitor withthe press line pressure between Example 2 and Example 3 is referred toas Example 10. Among electrolytic capacitors using foil type 3 having anetching magnification of 17 times and the oxide film was unformed,unpressed capacitor is referred to as Comparative Example 3, thencapacitors are referred to as Examples 4 to 6 in ascending order of thepress line pressure. Among electrolytic capacitors using foil type 4having an etching magnification of 22 times, unpressed capacitor isreferred to as Comparative Example 4, then capacitors are referred to asExamples 7 to 9 in ascending order of the press line pressure.

(Cathode Body Cross-Section Observation)

Cross sections of the cathode bodies of Comparative Example 1,Comparative Example 2, Examples 1 to 3, Example 5 and Example 8 werephotographed with a scanning electron microscope at a magnification of5,000 to obtain SEM images. The results are shown in FIGS. 2A to 8B.FIGS. 2A and 2B are SEM images of Comparative Example 1, in which FIG.2A shows a cathode body at the press line pressure of 0 Ncm⁻¹ and FIG.2B shows a cathode body at the press line pressure of 3.85 kNcm⁻¹. FIG.3 is an SEM image of Comparative Example 2. FIGS. 4A and 4B are an SEMimage of Example 1, FIGS. 5A and 5B are an SEM image of Example 2, FIGS.6A and 6B are an SEM image of Example 3, FIGS. 7A and 7B are an SEMimage of Example 5, and FIGS. 8A and 8B are an SEM image of Example 8.In FIGS. 4A to 8B, both A and B are the same image, however A shows theconvex portion length Lc, and B shows the unevenness depth Hf.

As shown in FIGS. 2A, 2B, and 3 , in the cathode bodies of ComparativeExample 1 and Comparative Example 2, the interface between the enlargedsurface layer and the carbon layer is substantially along the flat lineL. On the other hand, it is obvious by comparing FIGS. 4A and 4B to 8Aand 8B with respect to FIGS. 2A and B and 3, the cathode bodies ofExamples 1 to 3, Examples 5, and Example 8 are the interfaces betweenthe enlarged surface layer and the carbon layer are not along the flatline L, and it was confirmed that the outer surface unevenness waspresent, and the etching unevenness was also confirmed.

When the length Lc and height Hc of each convex region 1 to 6 confirmedfrom the SEM images of FIGS. 4A to 8B were measured and the porosity ofthe carbon layer was measured, the results shown in Table 3 below wereobtained. In the table, the unit of numerical values for length andheight is μm.

TABLE 3 Convex Exam- Exam- Exam- Exam- Exam- shape ple 1 ple 2 ple 3 ple5 ple 8 Length of 1.64 1.52 3.90 2.40 3.94 convex 1 Length of 1.63 7.645.25 2.26 7.38 comvex 2 Length of 1.84 5.45 2.67 7.25 2.27 convex 3Length of 6.40 2.48 3.63 4.22 1.72 convex 4 Length of 3.04 2.86 — 4.57 —convex 5 Length of — — — 1.98 — convex 6 Average 2.91 3.99 3.86 3.783.82 length Height of 0.34 0.37 0.34 0.54 0.52 convex 1 Height of 0.150.52 0.34 0.35 0.80 convex 2 Height of 0.16 0.46 0.38 0.50 0.63 convex 3Height of 0.40 0.30 0.30 0.46 0.29 convex 4 Height of 0.46 0.36 — 0.50 —convex 5 Height of — — — 0.20 — convex 6 Average 0.30 0.40 0.34 0.430.56 height Porosity 17.1% 14.1% 9.9% 8.6% 6.2%

As shown in Table 3, in detail, the cathode body of Example 1 is formedwith the outer surface unevenness with significant undulations within anappropriate range. The average length Lc of the convex region of theouter surface unevenness of Example 1 is as short as 2.91 μm, and theunevenness is steep. In the first embodiment, although the enlargedsurface layer is compressed as a whole, the degree of compressiondeformation is sparse, and it can be said that a region where thecompression deformation is large and a region where the compressiondeformation is small are conspicuous. In addition, some gaps remainbetween the carbon layer and the enraged surface layer. Although theetching unevenness is formed, many voids not filled with the carbonmaterial still remain in the etching pits, and the porosity of thecarbon layer is also high.

On the other hand, in the cathode bodies of Examples 2, 3, 5 and 8, theundulations of the outer surface unevenness becomes gentle within anappropriate range. The length LC of the convex region of the outersurface unevenness is as long as 3.99 μm, 3.86 μm, 3.78 μm and 3.82 μm.In Examples 2, 3, 5 and 8, the enlarged surface layer was compressed asa whole, the degree of compression deformation is approaching uniformly,however visually recognized as sparse, and the region where thecompression deformation is large and the region where the compressiondeformation is small remain. Almost no gap is confirmed between thecarbon layer and the enlarged surface layer. In addition, the etchingpit is filled with a large amount of carbon material, the voids areconsiderably reduced, and the porosity of the carbon layer is alsosmall. When the etching magnification becomes high as in Examples 5 and8, the porosity of carbon becomes low. Further, it is considered thatthe the etching magnification becomes high, the average height of theconvex portions becomes large, and the interface with the carbon layerundulates larger, so that good adhesion is exhibited.

Next, based on the photographs shown in FIGS. 2A to 8B, the penetrationdepth Hd of the carbon layer at any five points was measured in thecathode bodies of Comparative Example 1, Examples 1 to 3, Example 5 andExample 8 having the press line pressure of 3.85 kNcm⁻¹. That is, thedifference in the height direction from the deepest portion of thecarbon layer that further entered the etching pit from the concaveregion, to the apex of the convex region adjacent to the concave regionwas measured at five points. In addition, based on the photographs shownin FIGS. 2A to 8B, the unevenness depth of the uneven shape (outersurface unevenness) was measured in the cathode bodies of ComparativeExample 1, Examples 1 to 3, Example 5 and Example 8 having the pressline pressure of 3.85 kNcm⁻¹. The results are shown in Table 4.

TABLE 4 Penetration Comparative example 1 depth (Hd) (3.85 kNcm⁻¹)Example 1 Example 2 Example 3 Example 5 Example 8 First point 0.36 0.700.82 1.22 1.18 1.40 Second point 0.36 0.62 0.76 0.96 0.98 1.16 Thirdpoint 0.28 0.50 0.72 0.62 0.90 0.84 Fourth point 0.20 0.48 0.68 0.540.74 0.74 Fifth point 0.20 0.42 0.66 0.50 0.56 0.68 Average 0.28 0.540.73 0.77 0.87 0.96 Maximum 0.36 0.70 0.82 1.22 1.18 1.40 Minimum 0.200.42 0.66 0.50 0.56 0.68 Unevenness 0.36 0.53 0.68 0.97 0.97 1.35 depth(Hf)

As shown in Table 4, in Comparative Example 1 in which the press linepressure was 3.85 kNcm⁻¹, the penetration depth Hd was 0.28 μm onaverage. It was also found that the unevenness depth Hf of the outersurface unevenness was as small as 0.36 μm. This is because ComparativeExample 1 is unetched, so there is no room for entering the etching pit,and since it is not etched, it is difficult to compress and deform, andthere is no concave region. It also shows the degree of unevenness ofthe flat cathode foil.

On the other hand, in Example 1, the penetration depth is 0.54 μm ormore on average. Further, the unevenness depth Hf of the outer surfaceunevenness is 0.5 μm or more. In Examples 2, 3, 5 and 8, concave regionsare generated according to the density of the etching pits, and thecarbon material enters the etching pits from the concave regions, sothat the penetration depth is 0.7 μm or more on average. From this, itcan be seen that the outer surface unevenness of an appropriatepenetration promotes the generation of the etching unevenness.

Regarding the cathode bodies of Examples 4 and 7, the etchingmagnification of the cathode foil is higher than that of Example 1,however since the same press line pressure of 1.54 kNcm⁻¹ as in Example1 is applied, within the appropriate range, the outer surface unevennesswith significant undulations is formed. In addition, regarding thecathode bodies of Examples 6 and 9, since the etching magnification ofthe cathode foil is higher than that of Example 1 and the press linepressure of more than 3.85 kNcm⁻¹ is applied, within the appropriaterange, the outer surface unevenness with gentle undulations is formed,and the etching unevenness is also generated.

In addition, from the SEM images of FIGS. 2A to 8B, the ratio of theinterface length Y to the range length X was measured with respect tothe cathode bodies of Comparative Example 1 having the press linepressure of 0 kNcm⁻¹, Comparative Example 1 having the press linearpressure of 3.85 kNcm⁻¹, Comparative Example 2, Examples 1 to 3, 5 and8. Further, the ratio of the interface length Y to the range length Xwas also measured for the cathode body of Example 10. The results areshown in Table 5.

TABLE 5 Measured Etching Press line Range Interference Y/X × 100 imageFoil type magnification pressure (kNcm⁻¹) length (μm) length (μm) (%)Comparative FIG. 2A 1 1 0 26 26.00 100.0 Example 1 Comparative FIG. 2B 11 3.85 26 26.17 100.7 Example 1 Comparative FIG. 3 2 7 0 26 27.27 104.6Example 2 Example 1 FIG. 4 2 7 1.54 26 29.79 114.6 Example 2 FIG. 5 2 73.85 26 29.65 114.0 Example 10 — 2 7 5.38 26 30.91 118.9 Example 3 FIG.6 2 7 7.69 26 32.21 123.9 Example 5 FIG. 7 3 17 3.85 26 29.81 114.7Example 8 FIG. 8 4 22 3.85 26 34.33 132.0

As shown by the ratio of the interface length Y to the range length X inTable 5, in Comparative Example 1 and Comparative Example 2, the rangelength X and the interface length Y are almost the same, and the outersurface unevenness is not generated. On the other hand, it is obvious bycomparing Comparative Example 2 with Examples 1, 2, 3 and 10, it can beseen that the ratio of Examples 1, 2 and 10 was 110% or more, the outersurface unevenness was generated, and the surface area of the cathodebody was improved. Further, it is obvious by comparing Example 5 andExample 8, it can be seen that the outer surface unevenness was alsogenerated in Examples 5 and 8 and the surface area of the cathode bodywas improved.

Regarding the cathode bodies of Comparative Example 1 (press linepressure 0 kNcm⁻¹) and Comparative Example 2 which were not pressed,there was almost no unevenness depth of the outer surface unevenness,and the outer surface shape was substantially flat. Further, FIGS. 9A-9Ccomprise an SEM photograph when the cathode foil of the same foil typeas in Comparative Example 2 is pressed without a carbon layer, and FIG.9A shows no press, FIG. 9B shows the press line pressure of 3.85 kNcm⁻¹and FIG. 9C shows a case where the press line pressure is 7.69 kNcm⁻¹.As shown in FIGS. 9A-9C, even when the cathode foil was pressed whilethe carbon layer was absent, even if the press line pressure of 1.54kNcm⁻¹ or more was applied, the outer surface unevenness was notgenerated.

(Electrolytic Capacitor)

Next, in addition to the cathode bodies of Comparative Examples 1 to 4and Examples 1 to 9, Comparative Example 5 was prepared by using anetching-untreated plain foil as a substrate current collector, andforming a titanium nitride layer by an electron beam vapor depositionmethod. Electrolytic capacitors were produced using the cathode bodiesof Comparative Examples 1 to 5 and Examples 1 to 9.

In each electrolytic capacitor, an anode foil manufactured under commonconditions and various cathode bodies are opposed to each other via thesame separator, impregnated with an electrolytic solution prepared undercommon conditions to form a laminate cell, and a common reformationtreatment is performed. Specifically, for all electrolytic capacitors,the aluminum foil was etched to form a dielectric oxide film so that thenominal formation voltage was 4 Vfs, and an aluminum foil having aprojected area of 2.1 cm² was obtained, and this was used as an anodefoil. As the separator, rayon was used in all electrolytic capacitors.Further, as an electrolytic solution common to all electrolyticcapacitors, it was prepared by using tetramethylimidazolium phthalate asthe solute and γ-butyl lactone as the solvent. At the time ofreformation, a voltage of 3.35 V was applied for 60 minutes in anenvironment of 105° C. for all electrolytic capacitors.

(Capacitance Test)

Then, the electrolytic capacitors of Comparative Examples 1 to 5 andExamples 1 to 9 were subjected to no load at 20° C. (initial stage) anda load of 2.4 V DC under a 125° C. environment for 250 hours, then thecapacitance (Cap) at 120 Hz and 10 kHz charging/discharging (under loadin a high thermal environment) was measured. The results are shown inTable 6.

TABLE 6 Initial Characteristics under high Δ Cap characteristics thermalenvironment load ([B/A × 100)] Etching Press line Cap (μF): A Cap (μF):B [%]) Foil type magnification pressure (kNcm⁻¹) 120 Hz 10 kHz 120 Hz 10kHz 120 Hz 10 kHz Comparative 1 1 0 88.8 5.3 17.2 2.2 −80.6 −57.3Example 1 1.54 135.4 16.3 23.9 2.2 −82.4 −86.4 3.85 137.4 29.0 35.1 2.2−74.6 −92.4 7.69 153.5 49.2 76.5 2.3 −50.2 −95.3 Comparative 2 7 0 184.026.4 102.2 14.3 −44.6 −45.6 Example 2 Example 1 1.54 193.5 97.4 181.457.5 −6.3 −40.9 Example 2 3.85 199.8 97.8 185.7 82.4 −7.1 −16.8 Example3 7.69 193.7 96.0 178.4 83.0 −7.9 −13.5 Comparative 3 17 0 216.1 68.5153.2 31.5 −29.1 −54.0 Example 3 Example 4 1.54 224.0 107.3 202.3 54.0−9.7 −49.7 Example 5 3.85 229.9 106.3 208.5 94.2 −9.3 −11.4 Example 67.69 223.7 103.9 200.3 91.7 −10.5 −11.7 Comparative 4 22 0 205.6 50.594.1 37.6 −54.2 −25.6 Example 4 Example 7 1.54 219.6 105.8 202.3 81.9−7.9 −22.6 Example 8 3.85 232.7 104.5 213.1 93.6 −8.4 −10.4 Example 97.69 235.0 103.7 210.3 91.1 −10.5 −12.1 Comparative 0 230.1 89.9 166.258.2 −27.8 −35.4 Example 5

As can be seen by comparing Comparative Example 1 and ComparativeExample 5 in Table 6, compared to the electrolytic capacitors made ofthe cathode body deposited with titanium nitride, the electrolyticcapacitor composed of the carbon layer and the cathode foil and using anunetched plain foil was inferior in capacitance in all combinations ofinitial characteristics and characteristics under high thermalenvironment load, low frequency region and high frequency region, andthe rate of change of capacitance was not good either. Further, whenComparative Example 5 is compared with Comparative Examples 2 to 4, whenthe outer surface unevenness is not formed at the interface between theenlarged surface layer and the carbon layer even if the etchingtreatment is performed, almost all the measurement items were inferiorto the electrolytic capacitor made of the cathode body deposited withtitanium nitride.

On the other hand, as can be seen by comparing Comparative Examples 5and Examples 1 to 9, compared to the electrolytic capacitors using thecathode body deposited with titanium nitride, electrolytic capacitorswith outer surface unevenness formed at the interface between thecathode foil and the carbon layer, in the initial characteristics, thecapacitance due to charging/discharging at 10 kHz was improved. Further,as can be seen by comparing Comparative Examples 5 and Examples 8 and 9,due to the outer surface unevenness with gentle undulations and theetching unevenness that reaches a sufficient depth promoted by thisouter surface unevenness and high etching magnification, in the initialcharacteristics, the capacitance due to charging and discharging at 120Hz becomes larger than the electrolytic capacitor using the cathode bodydeposited with titanium nitride.

Furthermore, by comparing Comparative Examples 5 and Examples 1 to 9,compared to the electrolytic capacitors using the cathode body depositedwith titanium nitride, all electrolytic capacitors having outer surfaceunevenness formed at the interface between the carbon layer and theenlarged surface layer have a high capacitance in the loadcharacteristics under a high thermal environment when thecharge/discharge is 120 Hz. In particular, as can be seen by comparingComparative Examples 5 and Examples 1 to 9, regarding the rate ofincrease/decrease in capacitance when the load is applied to the initialcapacitance in the high temperature environment, when the outer surfaceunevenness is formed, the degree of decrease in capacitance wasdramatically suppressed in charging/discharging at 120 Hz.

Further, as can be seen by comparing Examples 2, 3, 5, 6, 8 and 9, dueto the outer surface unevenness with gentle undulations in theappropriate rage and the etching unevenness that reaches a sufficientdepth promoted by this outer surface unevenness, the rate ofincrease/decrease in capacitance during charging/discharging at 10 kHzwas dramatically suppressed.

From the above, the adhesion between the carbon layer and the enlargedsurface layer is improved by the outer surface unevenness, andregardless of whether it is in the low frequency region or the highfrequency region, whether it is the initial characteristic or the loadcharacteristic under the high temperature environment, it was confirmedthat the capacitance was improved and the thermal stability was alsoimproved. In particular, the presence of the outer surface unevennesshas higher thermal stability than the case where titanium nitride isdeposited on the cathode foil in the combination of the low frequencyregion and the high temperature thermal environment, and exhibits highcapacitance.

In addition, when the undulations of the outer surface unevenness isgentle, even in the high frequency region and high temperature thermalenvironment, it has higher thermal stability than the case wheretitanium nitride is deposited on the cathode foil, and exhibits highcapacitance. In addition, when the outer surface unevenness is with thegentle undulations and the etching magnification is high, in allcombinations of initial characteristics and characteristics under highthermal environment load, low frequency region and high frequencyregion, it exhibits a capacitance higher than the case where titaniumnitride is deposited on the cathode foil.

1. An electrode body used for a cathode of an electrolytic capacitor,comprising: a cathode foil made of aluminum material with a temper signof H, and having an enlarged surface layer formed on a surface; and acarbon layer formed on the enlarged surface layer, wherein: an interfacebetween the enlarged surface layer and the carbon layer has an unevenshape which is compressed and deformed, the enlarged surface layer isformed by digging a plurality of etching pits, and the carbon layerfurther enters into the etching pits from the interface of the unevenshape.
 2. The electrode body according to claim 1, wherein unevennessdepth of the uneven shape is 0.5 μm or more.
 3. The electrode bodyaccording to claim 1, wherein the carbon layer penetrates the etchingpit by an average of 0.5 μm or more in a depth direction.
 4. Theelectrode body according to claim 2, wherein the carbon layer penetratesthe etching pit by an average of 0.5 μm or more in a depth direction. 5.The electrode body according to claim 1, wherein the carbon layerpenetrates the etching pit by an average of 0.7 μm or more in a depthdirection.
 6. The electrode body according to claim 3, wherein thecarbon layer penetrates the etching pit by an average of 0.7 μm or morein a depth direction.
 7. The electrode body according to claim 4,wherein the carbon layer penetrates the etching pit by an average of 0.7μm or more in a depth direction.
 8. An electrolytic capacitor includingthe electrode body according to claim 1 as a cathode.
 9. An electrolyticcapacitor including the electrode body according to claim 2 as acathode.
 10. An electrolytic capacitor including the electrode bodyaccording to claim 3 as a cathode.
 11. An electrolytic capacitorincluding the electrode body according to claim 6 as a cathode.
 12. Anelectrolytic capacitor including the electrode body according to claim 7as a cathode.
 13. A method for manufacturing an electrode body used fora cathode of an electrolytic capacitor, comprising: a process of formingan enlarged surface layer on a surface of cathode foil made of aluminummaterial with a temper sign of H, wherein a plurality of etching pitsother than the uneven shape is dug in the enlarged surface layer; aprocess of forming a carbon layer on the enlarged surface layer, and aprocess of forming an uneven shape, which is compressed and deformed, onan interface between the enlarged surface layer and the carbon layerwhile making the carbon layer to further enter into the etching pitsfrom the interface of the uneven shape by pressing the cathode foil onwhich the carbon layer was formed.